JPS6391349A - Production of aromatic carboxylic acid or ester thereof - Google Patents

Abstract

PURPOSE:To obtain a corresponding 4-(halogenated phenyl)- or 4-(halogenated phenoxy)-benzoic acid inexpensively and in high yield, by reacting a halogenated- biphenyl or -diphenyl ether with CO in the presence of a basic compound. CONSTITUTION:A compound shown by formula I (X is Br or I; n is 1 or 0) is reacted with CO in the presence of a basic compound (e.g. aliphatic alkyl or alkali metallic hydroxide) to give a compound shown by formula II (R is H, alkyl or aromatic group). The reaction is generally carried out in the presence of a catalytic system containing a transition metal (e.g. Pd or Ni) or a compound thereof at 100-250 deg.C and when X is I, preferably the reaction is sufficiently advanced in a catalyst-free system. The reaction temperature in this case is 180-400 deg.C. Conversion ratio is suppressed to <=90% in order to obtain a monocarbonyl compound advantageously. The compound shown by the formula II is a basic raw material for heat-resistant, chemical-resistant polymers and liquid crystal compounds.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field) The present invention relates to a novel method for producing halogenated aromatic carboxylic acids or esters thereof. Comparison of target compound of the present invention 4
-C4-halogenated phenylbenzoic acid or its esters and 4-(4-/-logonated?enoxy)benzoic acid or its esters can be hydrolyzed to produce hydroxyluzenic acid, which is then subjected to alcoholysis. to produce a dialkoxycarboxylic acid, and by substitution with a cyano group, cyanocarTI? Generate /@. These compounds are used as raw materials for fibers and resins with poor heat resistance and chemical resistance, and are also used as basic raw materials for synthesizing various liquid crystal compounds.

(Prior art) Conventionally known manufacturing methods include, for example, 4-(4
- For iodophenoxy-9benzoic acid or its ester, Ivanova, V, M, et, al,
Zh, Org.

Khim, 1968.4 (10) 1836 (Rums
) J is known. That is, it is a method in which 4-iododiphenyl ether is reacted with MexNCOCl and then saponified. This method uses expensive raw materials and cannot be said to be an industrially valuable method. For other methods, few industrially valuable methods have been proposed.

(Means and effects for solving the problem) The present inventors
As a result of intensive research from the above viewpoint, we have found that using dibrominated or diiopurified piphenyl or diphenyl ether, which can be easily synthesized from inexpensive biphenyl or diphenyl ether, mono-ruzenylation is performed with carbon oxide to convert the two halogen groups of biphenyl or diphenyl ether. Calz one of the
It has been found that aromatic carzeneic acid or its ester can be easily obtained by using only inexpensive raw materials and in high yield by converting it into a hexacid or its ester. The present invention is based on the above findings, and r1 is 0 or 1).
This method is characterized by reacting a compound represented by the formula with carbon monoxide in the presence of a basic substance to obtain the general formula = 0 or 1, where R is hydrogen, an alkyl group, or an aromatic group.

The brominated or iodinated biphenyls or diphenyl ethers used as raw materials of the present invention are, for example, 4.4'-dibromidiphenyl, 4.4'-dibromidiphenyl ether, 4.4'-jotohyphenyl, 4.4' - It can be obtained by various methods such as jodder, nyl ether, etc.

Iodinated piphenyl or diphenyl ether.

It can be easily obtained by oxidative iodination of biphenyl or diphenyl ether.

That is, there are methods such as iodination in the presence of nitric acid, or iodination in the presence of Fi acid and hydrogen peroxide or oxygen. Also brominated biphenyl or diphenyl ether II
i. It is easily obtained by reacting biphenyl or hash phenyl ether with bromine at low temperature. These methods make it possible to advantageously produce para-substituted halides.

The carbonylation reaction of the present invention is generally carried out in the presence of a catalyst system containing a transition metal or a compound thereof for both iodides and bromides, and the reaction conditions are generally better for the carbonylation reaction of iodides. It is possible to make it considerably milder. Furthermore, in the case of brominated compounds, the reaction does not proceed unless a catalyst is used.

On the other hand, in the case of iodides, the reaction proceeds satisfactorily even in the absence of a catalyst if the reaction conditions are selected. In that sense.

It can be said that it is preferable to use an iodide as the raw material for the thickness.

Transition metals used in catalytic reactions include:
Generally, those active in car-2nylation reaction are used,
■Group transition metals, such as palladium, platinum, nickel,
Examples include conomalt, iron, manganese, etc., but from the viewpoint of yield, palladium, nickel, cobalt, and iron are preferably used. These transition metals themselves can be used, or their halides, sulfates, nitrates, organic acid salts, etc. can be used. Moreover, these transition metal compounds can also be used as a complex of -carbon oxide or a complex of phosphines such as triphenylphosphine.

The useful charge of the transition metal compound is 0.0% of the iodinated diphenyl or brominated diphenyl to be reacted. It is sufficient if it is in the range of 1 to 10 moles of O.

The basic substance to be used can be either an organic base or an inorganic base, as long as it can capture hydrogen iodide etc. generated in the reaction (for example, aliphatic amines, aromatic amines, hydroxylated amines, etc.). Quaternary ammonium, alcolades of alkali metals and alkaline earth metals, hydroxides of alkali metals and alkaline earth metals, alkali metal carbonates, combinations of aromatic or aliphatic carginic acids with alkali metals or alkaline earth metals Preferably, alkali metal salts of aliphatic amines, quaternary ammonium hydroxides, alkali metal hydroxides, alkali metal carbonate products can be used.The amount used is limited to specific circumstances. Preferably, the base is 0% relative to the aromatic halide, although not necessarily
．． #i is in the range of 2 to 10 equivalents, more preferably 0.4 to 3 equivalents.

If the carbonylation reaction is carried out in the presence of water, the corresponding carginic acid will be produced, and if carried out in the presence of alcohol, the corresponding carzenic acid ester will be produced.

When carried out in the presence of water, water is used alone or as a solvent system containing water.

As the solvent, a solvent that dissolves the raw material iodinated diphenyl or brominated diphenyl or a solvent that is soluble in both water can be used. For example, aliphatic fluorols such as methanol, ethanol, and pronognol, aromatic alcohols such as benzine alcohol, phenol, and 2,6-xylenol, hydrocarbons such as hexane, octane, benzene, and toluene, dimethylformamide, dimethylsulfoxyP and ethers such as dioxane. Furthermore, aliphatic amines and aromatic amines used as basic substances can also be used.

The amount of water used in the reaction is when water is used alone.

It is necessary to use at least 172 equivalents or more based on iodinated diphenyl or brominated diphenyl. Of course, there is no problem in using a large amount as a solvent. When used as a solvent system containing water, it is necessary to use the same amount as in the case of water alone, and it is better to mix it with other solvent systems, which has the effect of making the reaction system uniform. You can expect it.

When the reaction is carried out in the presence of an alcohol, the alcohol used can be selected depending on the desired ester. For example, aliphatic alcohols include methanol, ethanol, propatool, imbutanol, octatool, etc., and aromatic alcohols include tf propatool benzine alcohol, phenylphenol, phenoxyphenol, alkyl phenol, and naphthol. etc.Also, alcohol is not necessarily m
It doesn't have to be alcohol.

The carbon monoxide used in the carbonylation reaction may be pure carbon oxide, or may be diluted with other gases that do not adversely affect the reaction, such as nitrogen, argon, helium, or lower hydrocarbons. -The partial pressure of carbon oxide is o, i~
It is used in a range of 300 Kp/-1, preferably 1 to 200 Kp/i. If the pressure is too low, the reaction rate will be slow.
The yield also decreases. If the pressure is too high, side reactions will increase.

The reaction temperature at which the carbonylation reaction is carried out is slightly different depending on whether a catalyst is used or not.

In a reaction system using a catalyst, the reaction temperature is 50 to 300°C.
is preferably in the range of 0 to 250°C. When the temperature is low, the reaction rate is slow, and when the temperature is high, there are many side reactions.

In reaction systems that do not use catalysts, the reaction is preferably carried out at a temperature of 150'C or higher. More preferably Fii
It is carried out at a temperature of aoC or more and 400C or less. 150℃
At lower temperatures, the reaction rate is too slow to be practical, and at temperatures above 400°C, side reactions increase and the yield of the desired aromatic carzeneic acid decreases.

If the carnylation reaction is allowed to run uncontrolled to completion, both of the two halogen substituents of the biphenyl or diphenyl ether will be carnylated. Therefore, it is necessary to control the reaction midway. That is, in order to advantageously obtain a monocarbonylated product, it is necessary to stop one reaction midway through, and the conversion rate of the raw material dihalide is reduced to 9.
It is preferable to suppress it to 0.04 or less. More preferably 70
The goal is to keep it to a minimum.

The product after the carginylation reaction can be easily separated by recrystallization.

Next, the advantages of reacting diiodides in a non-catalytic system will be described. For example, when obtaining calzenic acid,
To illustrate the reaction in the case of aromatic monoiodite using an alkali metal salt of aromatic cargenic acid having the same skeleton as the aromatic carzenic acid to be generated as a base, the following reaction formula (1) It is expressed as

ArI +CO+H20+ArC00M→2 ArC0
OH+ MI (1) (In the formula, Ar represents an aromatic group and M represents an alkali metal atom.) In this case, the by-product is alkali metal iodide, which is easily soluble in water. However, since aromatic cargenic acid is generally solid and not easily soluble in water, the salt of hydrogen iodide and base can be removed by washing the reaction product with water. Of course, if too much base is used separately, the resulting aromatic carboxylic acid may also form a salt with the base. It is easy to separate as a solid.

For example, when obtaining an aryl carzenate ester, the following reaction formula is used to illustrate the reaction between an aromatic monoiodite and an alkali metal salt of an aromatic monohydroxy compound.

Ar I + Co + Ar' OM→Ar-C-0
-Ar'+M1 1! (In the formula, Ar and Ar' represent aromatic groups, and M represents an alkali metal atom.) In this case as well, only the alkali wire mesh iodide is produced as a by-product. Since it does not contain any other catalyst components and the by-product is a simple salt of an inorganic substance, it is very easy to separate the target aromatic carzenic acid aryl ester.

(Examples) Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited to these Examples.

Example 1 4.4'-Short diphenyl ether 6.33,9.
Tributylamine 6.66.9. Chloride/Crack A
0.18. li+.

Triphenylphosphine 0.39p, water 12.9p. 55-' of tetrahydrofuran was placed in a 100 stainless steel autoclave equipped with a stirrer, and after the inside of the autoclave was replaced with carbon monoxide, 25/- of carbon oxide was pressurized. After reacting at 125° C. for 12 minutes with stirring, the reaction was stopped by rapid cooling.

After the reaction was completed, unreacted carbon monoxide was purged, and the reaction solution was taken out and analyzed by gas chromatography and liquid chromatography. As a result, the conversion rate of 4.4'-short diphenyl ether was 824, and 4-(4
The selectivity Fi for -iodophenoxy)benzoic acid was 65%, and the selectivity for 1,1'-diphenyl ether-4,4'-dicarmenic acid was 30.

Example 2 The reaction was carried out in the same manner as in Example 1 except that the reaction time was changed from 12 minutes to 9 minutes. As a result, the conversion rate of 4.4'-short diphenyl ether was 63%, the selectivity of 4-(4-iodophenoxy)benzoic acid was 81%, and 1.1'-diphenyl ether-4,4'- The selectivity for dicallic acid was 12%.

Example 3 4.4'-dibrombiphenyl 15.69, n-)liptylamine 13.99, cobalt chloride 0.01. ) Riphenylphosphine 0.409, phenol so y
Total preparation, -carbon oxide pressure 30 and 2/-1 temperature 150℃
The reaction was carried out for 300 minutes. As a result, the conversion rate of 4,4'-brombiphenyl was 30%, and the selectivity of 4-(4-bromphenyl)benzoic acid was 89.

Example 4 4.4'-Short biphenyl 6,11! , tributylamine 6.7g, palladium chloride 0.18g, triphenylphosphine 0.39,9. Prepare 12g of water and ssg of tetrahydrofuran, -carbon oxide pressure 25M-97c
d. The reaction was carried out at a temperature of 115° C. for 10 minutes with stirring. As a result, the conversion rate of 4,4'-short biphenyl was 69%, the selectivity of 4,4'-biphenyl radical z7 acid was 25%, and the selectivity of 4-(4-iodophenyl)benzoic acid was 69%. I was in charge of 70.

Example 5 4.4'-Short diphenyl ether 42.2. ! 7
．． n-tributylamine 20.2,9. 1 g of nickel acetylacetonate, 1.57 g of triphenylphosphine, and 16.2.9 g of benzyl alcohol were charged, and the mixture was reacted at a carbon pressure of 30 Ki/cm and a temperature of 130° C. for 1 hour. As a result, the conversion rate of 4,4'-short diphenyl ether was 63%, and the selectivity of 4-(4-iodophenoxy)benzoic acid was 75%.

Example 6 4.41-Short biphenyl 13.5,9,4.4'
- Sodium biphenyl dicarphosphate19. li+, water 35! ! - Carbon oxide pressure 100KjiL/m
The reaction was carried out under stirring for 15 minutes at a temperature of 250°C. As a result, the conversion rate of 4.4'-short piphenyl was 48%, and the selectivity of 4-(4-iodophenyl)benzoic acid was in the BB range.

Example 7 4.41-Short diphenyl ether 14. j,? ,
Prepare 13 g of tri-n-butylamine and 35 g of water, - carbon oxide pressure 10 o1cy7'i, temperature 250 ° C.
The reaction was carried out under stirring for 20 minutes. As a result, 4.41-
The conversion rate of short diphenyl ether was 57%,
The selectivity of 4-(4-iodophenoxy)benzoic acid is 83
It was excellent.

Example 8 10.6 # of 4.4'-short diphenyl ether, 7 g of sodium phenoxide, and 3 to 9 of toluene were charged, the carbon oxide pressure was set to sly/-, and the reaction was carried out at a temperature of 200° C. for 15 minutes with stirring. As a result, the conversion rate of 4,4'-diiododiphenyl ether was 38% p,4-(
The selectivity of 4-iodophenoxy)benzoic acid phenyl ester was 87%.

Example 9 4.20.3 g of 4'-Jaw P biphenyl, sodium-2,6-dimethyl phenoxide9. lil,) Charge 301 toluene, - carbon oxide pressure to 50 to 7/-,
The reaction was carried out at a temperature of 200°C for 30 minutes under stirring under VC. As a result, the conversion rate of 4,4'-short piphenyl was 69, and the selectivity of 4-(4-iodophenyl)benzoic acid 2,6-dimethylphenyl ester was Hough 8.

Claims (1)

[Claims] 1. A compound represented by the following general formula (1) is reacted with carbon monoxide in the presence of a basic compound to form the following general formula (2).
Method for producing aromatic carboxylic acid or its ester represented by ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼・・・・・・・・・
・・・(1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
...(2) However, X is bromine or iodine, R is hydrogen, an alkyl group or an aromatic group, and n is 1 or 0. 2. A method according to claim 1 in which the conversion rate is kept to 90% or less. 3. A method according to claim 1 or 2 in which X is iodine and the reaction is carried out without using a catalyst.